WO2005105865A1

WO2005105865A1 - Process for the preparation of atactic 1-butene polymers

Info

Publication number: WO2005105865A1
Application number: PCT/EP2005/004506
Authority: WO
Inventors: Luigi Resconi; Simona Guidotti
Original assignee: Basell Polyolefine Gmbh
Priority date: 2004-05-04
Filing date: 2005-04-25
Publication date: 2005-11-10
Also published as: EP1753792A1; ATE445650T1; EP1753792B1; JP4897670B2; JP2007536421A; US8178636B2; US20090005523A1

Abstract

A process for obtaining atactic 1-butene polymer optionally containing at least one comonomer selected from ethylene, propylene or an alpha-olefin of formula CH2=CHR, wherein R is a linear or branched C3-C20 alkyl group, comprising the step of polymerizing 1-butene and optionally ethylene, propylene or said alpha-olefin, in the presence of a catalyst system obtainable by contacting: a) at least one metallocene compound of formula (I) in its meso or meso-like form wherein M is an atom of a transition metal; p is an integer from 0 to 3; X, same or different, is a hydrogen atom, a halogen atom, or a hydrocarbon group; L is a divalent C1-C40 hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R' and R2, are C1-C40 hydrocarbon radicals; T, equal to or different from each other, is a moiety of formula (IIa) or (Ilb) wherein R3 is a CI-C40 hydrocarbon radical; R4 and R6, are hydrogen atoms or C1-C40 hydrocarbon radicals; R5 is a CI-C40 hydrocarbon radical; R7 and R8, equal to or different from each other, are hydrogen atoms or C1-C40 hydrocarbon radicals; and b) an alumoxane or a compound capable of forming an alkyl metallocene cation.

Description

PROCESS FOR THE PREPARATION OF ATACTIC 1-BUTENE POLYMERS

The present invention relates to a process for the preparation of atactic and amorphous polymers of 1-butene, by polymerizing 1-butene and optionally an alpha-olefin in the presence of a metallocene catalyst component in the isomeric meso or meso like form. Amorphous polymers of 1-butene have been mainly used as sticking agents, improving agents for crystalline polyo-lefins and the like. They have been obtained by using different catalyst systems.

For example US 6,288,192 relates to amorphous polymers of 1-butene having ultra-high molecular weight, obtained by using compounds such as dichloro{2,2'-thiobis[4-methyl-6- (tert-butyl)phenolato]} titanium. These compounds are completely different from metallocene compounds. The document describes 1-butene polymers having a Mn of 200,000 or more, preferably of 300,000 or more, and more preferably of 500,000 or more. However, the Mn of the 1-butene polymers of the examples is much higher, in particular it ranges from about 1 million to about 3,5 millions. Even though the document states that a chain transfer agent such as hydrogen can be used to control the molecular weight, it is known from WO 02/060963 that the molecular weight of the polymers produced by thiobis(phenoxy)titanium dichlorides is relatively hydrogen insensitive. Therefore, it is not possible to lower the molecular weight of the 1-butene polymers below 1 million by using hydrogen as molecular weight regulator and consequently the disclosure of US 6,288,192 of Mn values of less than 1 million is considered not enabling. Moreover, even if US 6,288,192 does not relates about the NMR structure of the poly 1-butene obtained, in Journal of polymer Science: Part A: Polymer Chemistry, vol. 42, 1107-1111 (2004) the inventors analysed the polymer obtained with the process described in the US patent, showing that said polybutene obtained is slightly isotactic, with mmmm pentad content of about 25%.

In the US patent application 2003/0069320 1-butene polymers obtained by using double- bridged metallocene compounds are described. The 1-butene homo- and copolymers thus obtained are not completely amorphous, being characterised by at least one melting point. In Example 17 of EP 604908 a polybutene polymer by using dimethylsilanediylbis(9- fluorenyl) zirconium dichloride has been obtained. However this metallocene compounds has a C_2v symmetry and consequently it does not present the racemic and meso isomeric form. The polymer obtained ha a molecular weight (IN.) that can be further increased, and the catalyst activity was low. Amorphous propylene/ 1-butene copolymers by using metallocene compounds bearing one single cyclopentadienyl-substituent are described in JP 11-193309. The copolymers thus obtained are characterised by high propylene content.

In Macromol. Chem. Phys, 200, 1587- 1594 (1999) it is disclosed a process for polymerizing

1-butene in the presence of a rac/meso Me₂Si(2-Me-Ind)₂ZrCl₂. However the molecular weight of the atactic fraction of the obtained polymer reported in table 1 is very low.

In Macromol. Rapid Commun. 18, 581-589, (1997) a rac and meso mixture of dimethylsilylenebis(2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride has been used for polymerizing 1-butene. Also in this case the molecular weight of the atactic fraction is very low.

In Macromolecules 2000, 33, 1955-1959 a rac meso mixture of 3 different metallocene compounds, namely Me₂Si(2-Me-4,5-BzoInd)₂ZrCl₂, Me₂Si(2-Me-4-PhInd)₂ZrCl₂ and

Me₂Si(Ind) ZrCl₂ have been tested in 1-butene polymerization. However the molecular weight of the atactic polybutene and the activity can be still improved as shown in the comparative examples of the present application.

A new process that permits to obtain atactic and amorphous 1-butene polymers with high molecular weight and in high yield is therefore desirable.

An object of the present invention is a process for obtaining atactic and amorphous 1- butene polymers optionally containing at least one comonomer selected from ethylene, propylene or an alpha-olefin of formula CH₂=CHR, wherein R is a linear or branched C₃-

C₂₀ alkyl group, comprising the step of polymerising 1-butene and optionally ethylene, propylene or said alpha-olefin in the presence of a catalyst system obtainable by contacting: a) at least one metallocene compound of formula (I) in its meso or meso-like form

(I) wherein M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements; preferably M is titanium, zirconium or hafnium; p is an integer from 0 to 3, preferably p is 2, being equal to the formal oxidation state of the metal M minus 2;

X, same or different, is a hydrogen atom, a halogen atom, or a R, OR, OSO₂CF₃, OCOR, SR, NR₂ or PR₂ group, wherein R is a are linear or branched, cyclic or acyclic, Cι-C o-alkyl, C₂-C o alkenyl, C₂-C₄o alkynyl, C₆-C ₀-aryl, C₇-C o-alkylaryl or C₇-C o-arylalkyl radicals; optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R is a linear or branched -C^-alkyl radical; or two X can optionally form a substituted or unsubstituted butadienyl radical or a OR O group wherein R is a divalent radical selected from Cι-C₄₀ alkylidene, C₆-C o arylidene, C -C₄₀ alkylarylidene and C₇-C ₀ arylalkylidene radicals; preferably X is a hydrogen atom, a halogen atom or a R group; more preferably X is chlorine or a Ci- o-alkyl radical; such as methyl, or ethyl radicals;

L is a divalent Cι-C ₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements or a divalent silylidene radical containing up to 5 silicon atom; preferably L is a divalent bridging group selected from Cι-C₄o alkylidene, C₃-C₄₀ cycloalkylidene, C₆-C ₀ arylidene, C₇-C₄₀ alkylarylidene, or C₇-C ₀ arylalkylidene radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, and silylidene radical containing up to 5 silicon atoms such as SiMe₂, SiPh₂; preferably L is a group (Z(R")₂)_n wherein Z is a carbon or a silicon atom, n is 1 or 2 and R" is a C_!-C₂₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R" is a linear or branched, cyclic or acyclic, CrC^-alkyl, C₂-C₂o alkenyl, C₂-C₂₀ alkynyl, C₆-C₂o-aryl, C₇-C₂o-alkylaryl or C₇-C₂o-arylalkyl radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; more preferably the group (Z(R")₂)_n is Si(CH₃)₂, SiPr ,, SiPhMe, SiMe(SiMe₃), CH₂, (CKL and C(CH₃)₂;

R¹ and R², equal to or different from each other, are Cι-C ₀ hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably they are linear or branched, cyclic or acyclic, Cι-C ₀-alkyl, C₂-C ₀ alkenyl, C₂-C₄₀ alkynyl, C₆-C₄o-aryl, C₇-C o-alkylaryl or C -C ₀-arylalkyl radicals; optionally containing heteroatoms belonging to groups 13-17 of the Periodic

Table of the Elements; more preferably R¹ and R² are linear or branched, saturated or unsaturated C₁-C₂₀-alkyl radicals; more preferably R¹ and R² are methyl or ethyl radicals;

T, equal to or different from each other, is a moiety of formula (Ila) or (lib):

(Ha) (lib) wherein the atom marked with the symbol * bonds the atom marked with the same symbol in the compound of formula (I);

R is a Ci-C ₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R₃ is a linear or branched, cyclic or acyclic, Cι-C₄₀-alkyl, C₂-C ₀ alkenyl, C₂-C₄₀ alkynyl, C₆-C₄₀-aryl, C₇-C ₀-arylalkyl or a Cγ-Gto-alkylaryl radical; optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; more preferably R³ is a linear or branched, CrC^-alkyl C₆-C₄₀-aryl, C₇-C₄₀-arylalkyl radical; even more preferably R is a C6-C₂₀-aryl radical optionally substituted with one or more Ci-Cio alkyl groups;

R⁴ and R⁶, equal to or different from each other, are hydrogen atoms or Cι-C o hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R⁴ and R⁶, equal to or different from each other, are hydrogen atoms or linear or branched, cyclic or acyclic, d-C-_to-alkyl, C₂-C ₀ alkenyl, C₂-C₄o alkynyl, C₆-C ₀-aryl, C₇-C₄o-alkylaryl or C₇-C₄o-arylalkyl radicals; optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R⁴ and R⁶ are hydrogen atoms; R⁵ is a C C₄o hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R⁵ is a linear or branched, cyclic or acyclic, Cι-C₄₀-alkyl, C₂-C₄₀ alkenyl, C₂-C o alkynyl, C₆-C₄o-aryl, C -C ₀-alkylaryl or C₇-C₄₀-arylalkyl radicals; optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; more preferably R⁵ is a linear or branched, saturated or unsaturated Cι-C₂₀-alkyl radical; even more preferably R⁵ is a methyl or ethyl radical; 7 o R and R , equal to or different from each other, are hydrogen atoms or Cι-C₄₀ hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R⁷ and R⁸ are hydrogen atoms or linear or branched, cyclic or acyclic, Cι-C₄₀-alkyl, C₂-C₄₀ alkenyl, C₂-C ₀ alkynyl, C₆-C₄o-aryl, C₇-C₄o-alkylaryl or C₇-C₄₀-arylalkyl radicals; optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R⁸ is a hydrogen atom or a linear or branched, saturated or unsaturated C₁-C₂o-alkyl radical; more preferably R⁸ is a methyl or ethyl radical; preferably R⁷ is a Cι-C₄o-alkyl, C₆-C₄₀-aryl or a C -C₄₀-arylalkyl; more preferably R⁷ is a group of formula (III)

(III) wherein R⁹, R¹⁰, R¹¹, R¹² and R¹³, equal to or different from each other, are hydrogen atoms or linear or branched, cyclic or acyclic, -Qrø-alkyl, C₂-C₂o alkenyl, C₂-C₂o alkynyl, C₆-C₂o-aryl, C₇-C₂o-alkylaryl or C -C₂₀-arylalkyl radicals; optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R⁹, and R¹² are a hydrogen atoms; R¹⁰, R¹¹ and R¹³ are preferably hydrogen atoms or linear or branched, cyclic or acyclic, Ci-Cio-alkyl radicals; b) an alumoxane or a compound capable of forming an alkyl metallocene cation; and optionally c) an organo aluminum compound.

For the purpose of the present invention the term "meso form" means that the same substituents on the two cyclopentadienyl moieties are on the same side with respect to the plane containing the zirconium and the centre of the said cyclopentadienyl moieties. "Meso-like form" means that the bulkier substituents of the two cyclopentadienyl moieties on the metallocene compound are on the same side with respect to the plane containing the zirconium and the centre of the said cyclopentadienyl moieties as shown in the following compound:

In one embodiment, the compound of formula (I) has the following formula (IN)

(IN) wherein

M, X, p, L, R¹, R², R³, R⁴, R⁵ and R⁶ have the above described meaning. In an alternative embodiment the compound of formula (I) has the following formula (N)

(V) wherein M, X, p, L, R , R , R and R have the above described meaning. Metallocene compounds of formula (I) are well known in the art, they can be prepared according to known procedures, such as those described in WO 01/44318, WO 03/045964, PCT/EP02/13552 and DE 10324541.3.

Alumoxanes used as component b) can be obtained by reacting water with an organo- aluminium compound of formula HjAlU₃.j or HjAl₂U₆-j, where the U substituents, same or different, are hydrogen atoms, halogen atoms, d-C^-alkyl, C₃-C₂₀-cyclalkyl, C₆-C₂o-aryl, C - C₂o-alkylaryl or C -C₂o-arylalkyl radicals, optionally containing silicon or germanium atoms, with the proviso that at least one U is different from halogen, and j ranges from 0 to 1, being also a non-integer number. In this reaction the molar ratio Al/water is preferably comprised between 1:1 and 100:1.

The alumoxanes used in the process according to the invention are considered to be linear, branched or cyclic compounds containing at least one group of the type: U —O wherein the substituents U, same or different, are defined above. In particular, alumoxanes of the formula:

can be used in the case of linear compounds, wherein n¹ is 0 or an integer of from 1 to 40 and the substituents U are defined as above; or alumoxanes of the formula: u (Al — O)n² can be used in the case of cyclic compounds, wherein n² is an integer from 2 to 40 and the U substituents are defined as above.

Examples of alumoxanes suitable for use according to the present invention are methylalumoxane (MAO), tetra-(isobutyl)alumoxane (TIBAO), tetra-(2,4,4-trimethyl- pentyl)alumoxane (TIOAO), tetra-(2,3-dimethylbutyl)alumoxane (TDMBAO) and tetra-

(2,3,3-trimethylbutyl)alumoxane (TTMBAO).

Particularly interesting cocatalysts are those described in WO 99/21899 and in WOOl/21674 in which the alkyl and aryl groups have specific branched patterns.

Non-limiting examples of aluminium compounds that can be reacted with water to give suitable alumoxanes (b), described in WO 99/21899 and WOOl/21674, are: tris(2,3,3-trimethyl-butyl)aluminium, tris(2,3-dimethyl-hexyl)aluminium, tris(2,3-dimethyl- butyl)aluminium, tris(2,3 -dimemyl-pentyl)aluminium, tris(2,3 -dimethyl-heptyl)aluminium, tris(2-methyl-3 -ethyl-pentyl)aluminium, tris(2-methyl-3 -ethyl-hexyl)aluminium, tris(2-methyl-3-ethyl-heptyl)aluminium, tris(2-methyl-3-propyl-hexyl)aluminium, tris(2-ethyl-

3-methyl-butyl)aluminium, tris(2-ethyl-3-methyl-pentyl)aluminium, tris(2,3-diethyl- pentyl)aluminium, tris(2-propyl-3-methyl-butyl)aluminium, tris(2-isopropyl-3-methyl- butyl)aluminium, tris(2-isobutyl-3-methyl-pentyl)aluminium, tris(2,3,3-trimethyl- pentyl)aluminium, tris(2,3 ,3 -trimethyl-hexyl)aluminium, tris(2-ethyl-3 ,3 -dimethyl- butyl)aluminium, tris(2-ethyl-3 ,3 -dimemyl-pentyl)aluminium, tris(2-isopropyl-3 ,3 -dimethyl- butyl)aluminium, tris(2-trimethylsilyl-propyl)aluminium, tris(2-methyl-3-phenyl- butyl)aluminium, tris(2-ethyl-3 -phenyl-butyl)aluminium, tris(2,3 -dimethyl-3 -phenyl- butyl)aluminium, tris(2-phenyl-propyl)aluminium, tris[2-(4-fluoro-phenyl)-propyl]aluminium, tris[2-(4-ctøoro-phenyl)-propyl]aluminium, tris[2-(3-isopropyl-phenyl)-propyl]aluminium, tris(2-phenyl-butyl)aluminium, tris(3 -memyl-2-phenyl-butyl)aluminium, tris(2-phenyl- pentyl)aluminium, tris[2-(pentafluorophenyl)-propyl] aluminium, tris[2,2-diphenyl- ethyl] aluminium and tris[2-phenyl-2-methyl-propyl]aluminium, as well as the corresponding compounds wherein one of the hydrocarbyl groups is replaced with a hydrogen atom, and those wherein one or two of the hydrocarbyl groups are replaced with an isobutyl group.

Amongst the above aluminium compounds, trimethylaluminium (TMA), triisobutylaluminium

(TIBA), tris(2,4,4-trimethyl-ρentyl)aluminium (TIOA), tris(2,3-dimethylbutyl)aluminium (TDMBA) and tris(2,3,3- methylbutyl)aluminium (TTMBA) are preferred.

Non-limiting examples of compounds able to form an alkylmetallocene cation are compounds of formula D^E^", wherein D⁺ is a Brønsted acid, able to donate a proton and to irreversibly react with a substituent X of the metallocene of formula (I) and E^" is a compatible anion, which is able to stabilize the active catalytic species originating from the reaction of the two compounds, and which is sufficiently labile to be removed by an olefinic monomer.

Preferably, the anion E^" comprises one or more boron atoms. More preferably, the anion E^" is an anion of the formula BAr ^w, wherein the substituents Ar, which can be identical or different, are aryl radicals such as phenyl, pentafluorophenyl or bis(trifluoromethyl)phenyl.

Tetrakis-pentafluorophenyl borate is particularly preferred compound, as described in WO

91/02012. Moreover, compounds of formula BAr₃ can be conveniently used. Compounds of this type are described, for example, in the International patent application WO 92/00333.

Other examples of compounds able to form an alkylmetallocene cation are compounds of formula BAr₃P wherein P is a substituted or unsubstituted pyrrol radical. These compounds are described in WOO 1/62764. Compounds containing boron atoms can be conveniently supported according to the description of DE-A-19962814 and DE-A- 19962910. All these compounds containing boron atoms can be used in a molar ratio between boron and the metal of the metallocene comprised between about 1:1 and about 10:1; preferably 1:1 and 2.1; more preferably about 1:1.

Non limiting examples of compounds of formula D^Ε^" are:

Triethylammoniumtetra(phenyl)borate,

Tributylammoniumtetra(phenyl)borate,

Trimethylammoniumtetra(tolyl)borate,

Tributylammoniumtetra(tolyl)borate,

Tributylammoniumtetra(pentafluorophenyl)borate,

Tributylammoniumtetra(pentafluorophenyl)aluminate,

Tripropylammoniumtetra(dimethylphenyl)borate,

Tributylarnmoniumtetra(trifluoromethylphenyl)borate,

Tributylammoniumtetra(4-fluorophenyl)borate,

N,N-Dimethylbenzylammonium-tetrakispentafluorophenylborate,

N,N-Dimethylhexylamonium-tetrakispentafluorophenylborate,

N,N-Dimethylaniliniumtetra(phenyl)borate,

N,N-Diethylaniliniumtetra(phenyl)borate, N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate,

N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)aluminate,

N,N-Dimethylbenzylammonium-tetrakispentafluorophenylborate,

N,N-Dimethylhexylamonium-tetrakispentafluorophenylborate,

Di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,

Di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate,

Triphenylphosphoniumtetrakis(phenyl)borate,

Triethylphosphoniumtetrakis(phenyl)borate,

Diphenylphosphoniumtetrakis(phenyl)borate,

Tri(methylphenyl)phosphoniumtetrakis(phenyl)borate,

Tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate,

Triphenylcarbeniumtetrakis(pentafluorophenyl)borate,

Triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate,

Triphenylcarbeniumtetrakis(phenyl)aluminate,

Ferroceniumtetrakis(pentafluorophenyl)borate,

Ferroceniumtetrakis(pentafluorophenyl)aluminate.

Triphenylcarbeniumtetrakis(pentafluorophenyl)borate, and

N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate.

Organic aluminum compounds used as compound c) are those of formula HjAlU₃.j or

HjAl₂U₆._j as described above.

The polymerization process of the present invention can be carried out in liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in gas phase. Said hydrocarbon solvent can be either aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane). Preferably, the polymerization process of the present invention is carried out by using liquid 1-butene as polymerization medium. Preferably in bulk.

The polymerization temperature preferably ranges from 0°C to 250°C; preferably comprised between 20°C and 150°C and, more particularly between 40°C and 90°C;

The molecular weight distribution can be varied by using mixtures of different metallocene compounds or by carrying out the polymerization in several stages which differ as to the polymerization temperature and/or the concentrations of the molecular weight regulators and/or the monomers concentration. By carrying out the polymerization process using a combination of two different metallocene compounds of formula (I), a polymer endowed with a broad melting is produced.

Moreover, it has been surprisingly found that the activity of the catalyst system is increased when 1-butene is polymerised in presence of at least one comonomer selected from ethylene, propylene or an alpha-olefin of formula CH₂=CHR, wherein R is a linear or branched C₃-C₂₀ alkyl group. Therefore it is possible to increase the activity of the process of the present invention by adding even small amounts of comonomers selected from ethylene, propylene or said alpha-olefins. Preferably, 1-butene is polymerised in presence of up to 60% by moles, preferably up to 50 % by moles, more preferably 5-30 % by moles, of at least one of said comonomers. In a particularly preferred embodiment, the comonomer is a propylene, 1-pentene, 1-hexene, or 1-octene; more preferably the comonomer is propylene.

With the process of the present invention atactic and amorphous 1-butene homopolymers and copolymers endowed with high molecular weights can be obtained in high yields.

In particular in the 1-butene polymers obtained according to the present invention the enthalpy of fusion is not detectable at a differential scanning calorimeter (DSC), the polymers being completely amorphous. The atacticity of the 1-butene polymers obtainable with the process of the present invention is shown by the particular low value of the mmmm pentads; in particular the value of the mmmm pentads for the homopolymers is lower than 20.

A further object of the present invention is an atactic amorphous 1-butene homopolymer having the following characteristics:

(i) intrinsic viscosity (IN.) measured in tetrahydronaphtalene (THΝ) at 135°C equal to or higher than 1.30 dL/g; preferably the intrinsic viscosity is higher than 1.80 dL/g; more preferably higher than 2.0 dL/g; (ii) a distribution of molecular weight Mw/Mn lower than 4; preferably lower than 3.5; more preferably higher than 2.5 and lower than 3.5; (iii) no enthalpy of fusion detectable at a differential scanning calorimeter (DSC), (iv) isotactic pentad (mmmm) lower than 20% preferably lower than 15%: more preferably lower than 10%. As described above, with the process of the present invention it is possible to obtain in high yield 1-butene copolymers. Said copolymers are characterized by the fact to be completely atactic, i.e. even the 1-butene block in the polymer chain is atactic. Therefore the main effect of the comonomer is to increase the yield of the process and not to destroy the crystallinity of the resulting polymer, as usually happens when 1-butene is copolymerized by using catalyst system that produce crystalline polymers.

A still further object of the present invention is an atactic amorphous 1-butene copolymer containing up to 51% by moles, preferably up to 50% by moles of comonomer units derived from ethylene, propylene or an alpha-olefin of formula CH₂=CHR, wherein R is a linear or branched C₃-Cι₀ alkyl group, preferably comprising 5-30% by moles of ethylene, propylene or said alpha-olefin, having the following features:

(i) intrinsic viscosity (IN.) measured in tetrahydronaphtalene (THΝ) at 135°C of from 1.00 to 2.50 dl/g, preferably of from 1.79 to 2.31 dl/g; (ii) a distribution of molecular weight Mw/Mn lower than 4; preferably lower than 3.5; more preferably lower than 3; (iii) no enthalpy of fusion detectable at a differential scanning calorimeter (DSC). Preferably the comonomer derived units are selected from propylene, 1-pentene, 1-hexene, or 1-octene; still more preferably the comonomer units are propylene. The atactic amorphous 1-butene copolymer of the invention preferably has intrinsic viscosity (IN.) measured in tetrahydronaphtalene (THΝ) at 135°C of from 1.00 to 2.50 dl/g, , preferably of from 1.79 to 2.31 dl/g; provided that the viscosity is not from 1.78 to 1.79 dl/g or from 2.31 to 2.32 dl/g.

The atactic amorphous 1-butene copolymer of the invention is preferably endowed with a rlxr2 reactivity ratio measured as described in the example raging from 0.80 to 1.20; preferably ranging from 0.90 to 1.10; more preferably it ranges from 0.95 to 1.05. If the intrinsic viscosity (IN.) of the 1-butene copolymers of the invention is higher than 2.50 dl/g the processability of the copolymers decreases below acceptable values since the flowability of the melted polymer abruptly decreases. If the intrinsic viscosity is lower than 1.00 dl/g the atactic amorphous 1-butene copolymers of the invention are unacceptably sticky.

The atactic amorphous 1-butene homo- and copolymers obtainable by the process of the present invention, can be used as component for polymer compositions. In particular, due to the high molecular weight, they can be used in compositions comprising isotactic polypropylene homo or copolymers.

The following examples are given to illustrate and not to limit the invention. Examples The intrinsic viscosity (IN.) was measured in tetrahydronaphtalene (THΝ) at 135°C. Mw and Mn were calculated by using the following empirical equations:

Mw=59403(IN.)² + 137760(IN.)

Mn=32996(IN.)² + 53607(IN.)

The melting points of the polymers (T_m) were measured by Differential Scanning

Calorimetry (D.S.C.) on a Perkin Elmer DSC-7 instrument, according to the standard method.

A weighted sample (5-10 mg) obtained from the polymerization was sealed into aluminum pans and heated at 180°C with a scanning speed corresponding to 10°C/minute. The sample was kept at 180°C for 5 minutes to allow a complete melting of all the crystallites.

Successively, after cooling to 20°C with a scanning speed corresponding to 10°C/minute, and after standing 2 minutes at 20°C, the sample was heated for the second time at 180°C with a scanning speed corresponding to 10°C/min. In this second heating run, the peak temperature was taken as the melting temperature (T_m) and the area as enthalpy of fusion (ΔHf).

Molecular weight parameters and molecular weight distribution for all the samples were measured using a Waters 150C ALC/GPC instrument (Waters, Milford, Massachusetts,

USA) equipped with four mixed-gel columns PLgel 20 μm Mixed-A LS (Polymer

Laboratories, Church Stretton, United Kingdom). The dimensions of the columns were 300 x 7.8 mm. The solvent used was TCB and the flow rate was kept at 1.0 mL/min. Solution concentrations were 0.1 g/dL in 1,2,4 trichlorobenzene (TCB). 0.1 g/L of 2,6- di-t-butyl-4- methyl phenol (BHT) was added to prevent degradation and the injection volume was 300 μL. All the measurements were carried out at 135°C. GPC calibration is complex, as no well-characterized narrow molecular weight distribution standard reference materials are available for 1-butene polymers. Thus, a universal calibration curve was obtained using 12 polystyrene standard samples with molecular weights ranging from 580 to 13,200,000. It was assumed that the K values of the Mark-Houwink relationship were: Kps = 1.21 x 10^"4 dL/g and K_PB = 1.78 x 10^"4 dL/g for polystyrene and poly-1-butenes respectively. The

Mark-Houwink exponents a were assumed to be 0.706 for polystyrene and 0.725 for poly-

1-butenes. Even though, in this approach, the molecular parameters obtained were only an estimate of the hydrodynamic volume of each chain, they allowed a relative comparison to be made.

ΝMR analysis. ¹³C-ΝMR spectra were acquired on a DPX-400 spectrometer operating at

100.61 MHz in the Fourier transform mode at 120 °C. The samples were dissolved in l,l,2,2-tetrachloroethane-d2 at 120 °C with a 8% wt/v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD (waltzlό) to remove 1H-¹³C coupling. About 3000 transients were stored in 32K data points using a spectral window of 6000 Hz. The isotacticity of metallocene-made PB is measured by ¹³C

NMR, and is defined as the relative intensity of the mmmm pentad peak of the diagnostic methylene of the ethyl branch. This peak at 27.73 ppm was used as internal reference.

Pentad assignments are given according to Macromolecules, (1992), 25, 6814-6817.

The copolymer composition has been determined from the diads as follows:

PP = [Sαα (47.5-45.9 ppm)/Σ(Sαα)]xl00

PB = [Sαα (44.1-42.8 ppm)/Σ(Sαα)] l00

BB = [Sαα (39.93-40.31 ppm)/Σ(Sαα)]xl00

Σ(Sαα) = sum of Sαα peak areas = Sαα (47.5-45.9 ppm)+ Sαα (44.1-42.8 ppm)+ Sαα (

39.93-40.31 ppm)

P = PP+0.5PB

B = BB+0.5PB

Determination of the product of the reactivity ratios rlxr2

The product of reactivity ratios are obtained from C NMR triad distribution according to C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 10, 536 (1977) using the following expressions.

Butene/propylene copolymers:

Metallocene compounds meso dimethylsilandiylbis-6- [2,5 -dimethyl-3 -(2 ' -methyl-phenyl)cyclopentadienyl- [ 1 ,2-b] - thiophene] zirconium dichloride (A-l) was prepared according to WO 01/44318 rac dimethylsilylbis(2, 4, 6 trimethyl-indenyl) zirconium dichloride (A-2rac) was prepared according to Journal of Polymer science: Part A: polymer chemistry, vol 38, 4299-4307

(2000), dimethylsilylbis(2, 4, 6 trimethyl-indenyl) zirconium dichloride (A-2) was prepared according to the following procedure, it is obtained in rac meso 60:40 mixture:

Synthesis of Me2Si(2,4,6-trimethylindenyl)2ZrCl2

Synthesis of 2,4,6-trimethyl-indan-l-one A 500 mL, 3 -neck rounded bottom flask equipped with a magnetic stirring bar and a reflux condenser, was filled with nitrogen atmosphere and charged with 71.16 g of A1C1₃ (0.53 mol, 2.3 eq.) dissolved in 240 mL of chlorobenzene. At room temperature 28.38 mL of m- xylene (0.23 mol, 1 eq.) were added dropwise obtaining a light yellow suspension. The flask was then cooled to 0°C and 28.68 mL of 2-bromoisobutyryl bromide (0.23 mol, 1 eq.) were slowly added. At the end of the addition a dark-red slurry was obtained. The reaction mixture was then allowed to warm up to r.t. and stirred for 2 hours. Then it was transferred into a flask containing a solution of ice/HCl 37% = 3/1. The organic phase was extracted with Et O (3 x 200 mL): the combined organic phases were dried over Na₂SO , filtered and the solvent was removed in vacuo. An orange oil was obtained as product (37.48 g, yield 93.5%). The latter was used as such without further purification in the next step.

Synthesis of 2,4,6-trimethylindan-l-ol

37.48 g of 2,4,6-trimethyl-indan-l-one (0.215 mol) were dissolved in 200 mL of EtOH in a 500 mL, 3-neck rounded bottom flask equipped with a magnetic stirring bar, a thermometer and a reflux condenser. NaBH₄ (15.01 g, 0.394 mol, 1.6 eq) was then slowly added keeping the temperature below 20°C during the addition. The light yellow suspension was stirred at r.t. for 18 h. Then 100 mL of acetone were cautiously added and then the solvents were removed to give a white solid. The latter was treated with 100 mL of water and extracted with toluene (2 x 150 mL). The water phase was further extracted with toluene, the organic phases were combined and washed with a 10% aqueous solution of NH₄C1. After washing, the organic phase was dried over Na₂SO , filtered and evaporated to give 35.57 g of a yellow sticky solid, which resulted to be by NMR analysis the desired product as 1.4/1 mixture of two diastereoisomers, contaminated by 5% wt. of starting indanone (yield 89.2%). The product was used as such without further purification in the next step.

Synthesis of 2,4,6-trimethyl-indene

The 2,4,6-frimethyl-indan-l-ol, prepared as above described (35.57 g, 0.192 mol), 0.5 g of 7-toluenesulfonic acid monohydrate and 160 mL of toluene were placed in a 500 mL, 3- neck rounded bottom flask equipped with a magnetic stirring bar, a dean-Stark apparatus and a reflux condenser. The reaction mixture was heated at 80°C for 3 h and 3.5 mL of water were collected. Then the reaction mixture was cooled to room temperature and treated with a saturated NaHCO₃ aqueous solution: the organic layer was separated, the aqueous layer extracted with Et₂O and the organic phases collected. After drying over Na₂SO₄, the solvent was evaporated in vacuo giving 28.46 g of an orange oil, which resulted to be the desired product by proton NMR analysis (purity 93.7% by GC-MS) contaminated by 2.0% wt. of indanone, coming from the 2,4,6-trimethylindan-l-ol step (yield 87.8%). The product was used as such in the next step without further purification. Synthesis of Me₂Si(2,4,6-trimethylindenyl)₂ZrCl2.

5 g of 2,4,6-trimethylindene (31.6 mmol) were dissolved in 100 mL of Et₂O, the solution was cooled to 0 °C, and 13.27 mL of a 2.5 M solution of BuLi in hexane (33.2 mmol, 1.05 eq) added dropwise to it. The ice bath was removed and the reaction mixture was stirred for 1 hour. The creamy yellow slurry so obtained was cooled to 0°C, and to it were added dropwise 1.92 mL of Me₂SiCl₂ (16.5 mmol) in 20 mL of THF. After warming at room temperature, the yellow slurry was stirred for 1 h 30 min, then the solvents were removed under reduced pressure, and the residue was taken up in toluene, filtered over a G4 frit, and the residue washed with additional toluene until the filtrate was colourless (total 300 mL of toluene). The filtrate was evaporated to dryness in vacuo, to give 5.8 g of a brown oil, that proton NMR analysis confirmed to be the target ligand. This product (15.56 mmol) was dissolved into 100 mL of Et₂O, cooled to 0°C, and to it 12.6 mL of BuLi 2.5 M in hexane (31.5 mmol) were added dropwise. At the end of the addition, the red solution was allowed to reach room temperature, stirred for one additional hour, then cooled to 0°C. To it, a slurry of 3.67 g of ZrCl₄ (15.75 mmol) in 50 mL of toluene was added dropwise. The ice bath was removed, and after 2 hours stirring at room temperature, the thick yellow suspension was brought to dryness, taken up in toluene and filtered over a G4 frit. The dark filtrate was analyzed by proton NMR, dried, and slurried in a mixture of Et₂O (20 mL) and toluene (20 mL), filtered, and the solid residue (1.7 g) analyzed by proton NMR: the analysis confirms the formation of the target metallocene, in a meso:rac ratio of 60:40. meso dimethylsilylbis(2-methyl-4, 5 benzo-indenyl) zirconium dichloride (C-l) was prepared according to USP 5,830,821. meso dimethylsilylbis(2-methyl-4-phenyl-indenyl) zirconium dichloride (C-2) was prepared according to USP 5,786,432.

The cocatalyst methylalumoxane (MAO) was a commercial product which was used as received: Crompton AG, 10 %wt/vol toluene solution, 1.7 M in Al for Examples 1-6 and Comparatives Examples 1-2; Albemarle 30% wt./wt. in toluene for Examples 7-9. Examples 1-6 and comparative examples 1-2 The catalyst mixture was prepared by dissolving the amount of the metallocene indicated in table 1 in 4-8 ml of toluene with the proper amount of the MAO solution (Al(MAO)/Zr ratios are reported in table 1), obtaining a solution which was stirred for 10 min at room temperature before being injected into the autoclave.

6 mmol of Al(t-Bu)₃ (TIB A) (as a 1 M solution in hexane) and 1350 g of 1-butene were charged, at room temperature, in a 4-L jacketed stainless-steel autoclave, equipped with magnetically driven stirrer and a 35-mL stainless-steel vial, connected to a thermostat for temperature control, and previously purified by washing with an Al(/-Bu)₃ solution in hexanes and dried at 50°C in a stream of nitrogen. The autoclave was then thermostatted at the polymerization temperature reported in table 1 and the catalyst system, prepared as reported above, was injected in the autoclave by means of nitrogen pressure through the stainless-steel vial. The polymerization was carried out at constant temperature, for 1 hour. Then stirring is interrupted; the pressure into the autoclave is raised to 20 bar-g with nitrogen. The bottom discharge valve is opened and the 1-butene/poly- 1-butene mixture is discharged into a heated steel tank containing water at 70°C. The tank heating is switched off and a flow of nitrogen at 0.5 bar-g is fed. After cooling at room temperature, the steel tank is opened and the wet polymer collected. The wet polymer is dried in an oven under reduced pressure at 70° C.

The polymerization conditions and the characterization data of the obtained polymers are reported in Table 1.

In examples 5 and 6 instead of a pure meso form of A-2 a mixture of 60 meso and 40 racemic forms has been used. We tested the racemic form of A-2 (A-2rac) and it resulted to be inactive in butene polymerization. Therefore in examples 5 and 6 the activities are calculated with respect to the pure meso. This is a further advantage of the process of the present invention when compound A-2 is used because it is not necessary to divide the racemic form from the meso form, the racemic being inactive, but the metallocene compound can be used as such without the need of purification. Table 1

* comparative

^■+ polymerization time 120 min.

# meso:rac 60:40 n.d.= not detectable n.a.= not available

Examples 7-9

The catalyst/cocatalyst mixture was prepared by pre-reacting 5.2 ml of MAO 30% wt. in toluene with Triisobutylaluminium (TIB A) in isododecane (110 g/L solution - A1 _AO/A1_TIBA ⁼2/1 mole/mole); the mixture was stirred for 1 h at room temperature. After adding additional isododecane to reach a total organometallic compounds content of 100 g/L, the toluene/isododecane solution was slowly added at room temperature to the metallocene, yielding a clear red-orange catalytic solution after 10 min stirring. The concentration of A-l in the catalytic solution was 1.64 mg/1.

6 mmol of Al(i-Bu)3 (as a 1M solution in hexane) and the amounts of monomers listed in Table 2 were charged at room temperature in a 4-L jacketed stainless-steel autoclave, equipped with magnetically driven stirrer and a 35 -ml stainless-steel vial, connected to a thermostat for temperature control, previously purified by washing with an Al(i-Bu)3 solution in hexanes and dried at 50°C in a stream of nitrogen. No further monomers were fed during the polymerization.

The autoclave was then thermostated at the polymerization temperature of 60°C, and then the solution containing the catalyst/cocatalyst mixture was injected in the autoclave by means of nitrogen pressure through the stainless-steel vial, and the polymerization carried out at constant temperature for lh. Then stirring is interrupted; the pressure into the autoclave is raised to 20 bar-g with nitrogen. The bottom discharge valve is opened and the 1-butene/ 1-butene copolymer mixture is discharged into a heated steel tank containing water at 70°C. The tank heating is switched off and a flow of nitrogen at 0.5 bar-g is fed. After cooling at room temperature, the steel tank is opened and the wet polymer collected. The wet polymer is dried in an oven under reduced pressure at 70°C.

Table 2

n.d.= not detectable n.a. not available

Claims

1. A process for obtaining an atactic 1-butene polymer optionally containing at least one comonomer selected from ethylene, propylene or an alpha-olefin of formula CH₂=CHR, wherein R is a linear or branched C₃-C₂₀ alkyl group, comprising the step of polymerizing 1-butene and optionally ethylene, propylene or said alpha-olefin, in the presence of a catalyst system obtainable by contacting: a) at least one metallocene compound of formula (I) in its meso or meso-like form

(I) wherein M is an atom of a transition metal selected from those belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups in the Periodic Table of the Elements; p is an integer from 0 to 3, being equal to the formal oxidation state of the metal M minus 2; X, same or different, is a hydrogen atom, a halogen atom, or a R, OR, OSO₂CF₃, OCOR, SR, NR₂ or PR₂ group, wherein R is a are linear or branched, cyclic or acyclic, Cι-C₄o-alkyl, C₂-C₄0 alkenyl, C2-C₄0 alkynyl, C₆-C₄o-aryl, C₇-C₄₀-alkylaryl or C -C o-arylalkyl radicals; optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; or two X can optionally form a substituted or unsubstituted butadienyl radical or a OR O group wherein R is a divalent radical selected from C₁-C₄₀ alkylidene, C6-C₄0 arylidene, C₇-C₄₀ alkylarylidene and C₇-C ₀ arylalkylidene radicals; L is a divalent Cι-C ₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements or a divalent silylidene radical containing up to 5 silicon atom; R¹ and R², equal to or different from each other, are Cι-C₄o hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; T, equal to or different from each other, is a moiety of formula (Ila) or (lib):

(Ha) (lib) wherein the atom marked with the symbol * bonds the atom marked with the same symbol in the compound of formula (I); R is a Cι-C₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R⁴ and R⁶, equal to or different from each other, are hydrogen atoms or -C₄₀ hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R⁵ is a C1-C40 hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; and R , equal to or different from each other, are hydrogen atoms or Cι-C ₀ hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; and b) an alumoxane or a compound capable of foiming an alkyl metallocene cation;

2. The process according to claim 1 wherein the catalyst system further contains c) an organo aluminum compound.

3. The process according to claims 1 or 2 wherein in the compound of formula (I) M is titanium, zirconium or hafnium; X is a hydrogen atom, a halogen atom or a R group, wherein R has been defined as in claim 1; p is 2; and L is a divalent bridging group selected from Cι-C ₀ alkylidene, C₃-C ₀ cycloalkylidene, C6-C₄0 arylidene, C₇-C ₀ alkylarylidene, or C₇-C ₀ arylalkylidene radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, and silylidene radical containing up to 5 silicon atoms.

4. The process according to anyone of claims 1-3 wherein L is a group (Z(R")₂)_n wherein Z is a carbon or a silicon atom, n is 1 or 2 and R" is a -C₂₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements.

5. The process according to anyone of claims 1-4 wherein R¹ and R² are linear or branched, saturated or unsaturated Cι-C2o-alkyl radicals; R³ is a linear or branched, C₁-C₂o-alkyl Ce-C-io-aryl, C₇-C₄o-arylalkyl radical; R⁴ and R⁶ are hydrogen atoms; R⁵ is a linear or branched, saturated or unsaturated Cι-C2₀-alkyl radical; R⁸ is a hydrogen atom or a linear or branched, saturated or unsaturated Cι-C₂o-alkyl radical; and R⁷ is a C₁-C₄o-alkyl, C₆-C₄o-aryl or a C₇-C₄o-arylalkyl radical.

6. The process according to claim 5 wherein R⁷ is a group of formula (III)

wherein R⁹, R¹⁰, R¹¹, R¹² and R¹³, equal to or different from each other, are hydrogen atoms or linear or branched, cyclic or acyclic, Cι-C₂o-alkyl, C₂-C₂₀ alkenyl, C₂-C₂o alkynyl, C₆-C₂o-aryl, C₇-C₂o-alkylaryl or C₇-C₂o-arylalkyl radicals; optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements. The process according to anyone of claims 1-6 wherein the metallocene compound in its meso or meso-like form has formula (IV):

(IV) wherein M, X, p, L, R¹, R², R³, R⁴, R⁵ and R⁶ have the meaning described in claim 1.

8. The process according to anyone of claims 1-6 wherein the metallocene compound in its meso or meso-like form has formula (N):

wherein M, X, p, L, R¹, R², R⁷ and R⁸ R⁶ have the meaning described in claim 1.

9. The process according to anyone of claims 1-8 wherein 1-butene is copolymerized in presence of at least one comonomer selected from ethylene, propylene or an alpha- olefin of formula CH2=CHR, wherein R is a linear or branched C3-C20 alkyl group.

10. The process according to claim 9 wherein 1-butene is polymerized in presence of propylene.

11. An atactic amorphous 1-butene homopolymer having the following characteristics: (i) intrinsic viscosity (IN.) measured in tetrahydronaphtalene (THΝ) at 135°C equal to or higher than 1.30; (ii) distribution of molecular weight Mw/Mn lower than 4; (iii) no enthalpy of fusion detectable at a differential scanning calorimeter (DSC), (iv) isotactic pentad (mmmm)lower than 20%.

12. The atactic amorphous 1-butene homopolymer according to claim 9 wherein the distribution of molecular weight Mw/Mn is lower than 3.5; and the isotactic pentads (mmmm) are lower than 15%.

13. An atactic amorphous 1-butene copolymer containing up to 51% by moles of comonomer units derived from ethylene, propylene or an alpha-olefin of formula CH₂=CHR, wherein R is a linear or branched C₃-Cιo alkyl group having the following features: (i) intrinsic viscosity (IN.) measured in tetrahydronaphtalene (THΝ) at 135°C of from 1.00 to 2.50 dl/g; (ii) a distribution of molecular weight Mw/Mn lower than 4; preferably lower than 3.5; more preferably lower than 3; (iii) no enthalpy of fusion detectable at a differential scanning calorimeter (DSC).

14. The atactic amorphous 1-butene copolymer according to claim 13 comprising up to 50% by moles of comonomer units.

15. The atactic amorphous 1-butene copolymer according to claim 14 comprising 5-30% by moles of comonomer units.

16. The atactic amorphous 1-butene copolymer according to anyone of claims 13-15 wherein the comonomer units are propylene.

17. The atactic amorphous 1-butene copolymer according to anyone of claims 13-16 further characterized by a rlxr2 reactivity ratio ranging from 0.8 to 1.2